US7507135B2 - Method of manufacturing field emitter - Google Patents

Method of manufacturing field emitter Download PDF

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Publication number
US7507135B2
US7507135B2 US11/048,809 US4880905A US7507135B2 US 7507135 B2 US7507135 B2 US 7507135B2 US 4880905 A US4880905 A US 4880905A US 7507135 B2 US7507135 B2 US 7507135B2
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Prior art keywords
substrate
mixture
conductive layer
layer
field emission
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Expired - Fee Related, expires
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US11/048,809
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English (en)
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US20050176336A1 (en
Inventor
Sang-hyun Lee
Jeong-hee Lee
Shang-hyeun Park
Tae-Won Jeong
Jung-Na Heo
Won-seok Kim
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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Assigned to SAMSUNG SDI CO., LTD. reassignment SAMSUNG SDI CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEO, JUNG-NA, JEONG, TAE-WON, KIM, WON-SEOK, LEE, JEONG-HEE, LEE, SANG-HYUN, PARK, SHANG-HYEUN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/304—Field-emissive cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/304—Field emission cathodes
    • H01J2201/30446—Field emission cathodes characterised by the emitter material
    • H01J2201/30453—Carbon types
    • H01J2201/30469—Carbon nanotubes (CNTs)

Definitions

  • the present invention relates to a method of manufacturing a field emitter, by which method a large field emitter having an excellent adhesion is simply formed on a metal electrode.
  • a conventional field emitter has been used in various fields according to a field emission characteristic and a field emission effect thereof.
  • carbon nanotubes were developed in the early 1990's, much research into the manufacture of field emission displays using a carbon nanotube thin films has been conducted.
  • carbon-family materials including carbon nanotubes have poor adhesion to a substrate formed of silicon, glass, or the like. Hence, forming a film of carbon-family materials on a substrate is difficult. Even when the film is formed and used as a field emission emitter for a long period of time, the carbon nanotubes may be detached from the substrate due to low adhesion of the film. Hence, manufacturing of a wide field emitter is difficult.
  • a first method involves growing carbon nanotubes from a substrate, and a second method involves mechanically forming carbon nanotubes on a substrate by pasting the substrate with grown carbon nanotubes.
  • the second method When the second method is used, many impurities, such as, a binder, a resin, a filter, or the like, are included in the carbon nanotubes.
  • the impurities adversely affect field emission by the carbon nanotubes, and have a bad influence upon the durability and stability of the field emitter. While mechanical polishing, such as milling, is performed, many defects are detected. As a result, the life span of the field emitter is short.
  • materials other than carbon nanotubes When materials other than carbon nanotubes are used as field emission materials, they also may have low adhesion to a lower substrate or an electrode. The low adhesion of the field emission materials directly affects the performance and durability of the field emission display.
  • the present invention provides a method of manufacturing a large-area carbon nanotube field emitter, by which method adhesion between a field emission material, such as carbon nanotubes, and an electrode is improved, and the durability and field emission of the field emitter are also improved.
  • a method of manufacturing a field emitter includes the steps of: forming a patterned conductive layer on a substrate; coating an upper surface of the conductive layer with a mixture of a field emission material and metal powder; thermally treating the mixture to improve an adhesion of the mixture to the conductive layer; and removing a field emission material and a metal deposited on a portion other than the conductive layer.
  • the field emission material may be a carbon-family material, a metal or a semiconductor material.
  • the carbon-family material may include at least one of carbon nanotubes and a carbon horn.
  • the step of forming the patterned conductive layer includes: forming a photoresist layer so as to expose a predetermined upper area of the substrate; coating the exposed upper area of the substrate and an upper surface of the photoresist layer with a conductive material; and forming a conductive layer by removing the photoresist layer and a conductive material deposited on the photoresist layer.
  • the steps of coating the upper surface of the conductive layer with the mixture and thermally treating the mixture include: coating an exposed portion of the substrate and the conductive layer with a mixture of the field emission material, the metal powder and a suitable solvent at a predetermined ratio; and thermally treating the mixture at a temperature of about 600° C. so as to increase adhesion between the mixture and the conductive layer.
  • the metal powder may be silver, copper, zinc or nickel.
  • the diameter of the metal powder may be about 0.01 to 100 ⁇ m.
  • the mixture of the field emission material, the metal powder, and the solvent may be coated on the exposed portion of the substrate and the conductive layer using spin coating or printing.
  • the substrate may be a silicon substrate, a glass substrate, or an indium tin oxide substrate.
  • FIGS. 1A through 1G are cross-sectional views illustrating a method of manufacturing a field emitter according to an embodiment of the present invention
  • FIGS. 2A and 2B are pictures of a field emitter which is fabricated using carbon nanotubes as a field emission material in a method according to an embodiment of the present invention
  • FIG. 3A is a graph showing emitted fields of conventional field emitters that use carbon nanotubes as field emission materials, and an emitted field of a field emitter according to an embodiment of the present invention that uses carbon nanotubes as a field emission material, versus an applied voltage;
  • FIG. 3B is a graph showing emitted fields of a conventional field emitter that use carbon nanotubes, and a field emitter according to an embodiment of the present invention that use carbon nanotubes, versus time.
  • FIGS. 1A through 1G are cross-sectional views illustrating a method of manufacturing a field emitter according to an embodiment of the present invention.
  • a patterned photoresist (PR) layer 12 is formed on a substrate 11 and is exposed and patterned to form grooves 12 ′, each having a predetermined width.
  • the grooves 12 ′ indicate locations where a field emission material is formed.
  • each of the grooves 12 ′ has a predetermined shape.
  • This process is not necessary for formation of a single field emitter but is necessary for formation of a plurality of field emitters on a single substrate so as to manufacture a field emitter array for mass production of field emitters.
  • the type of substrate 11 used is not limited, so that a glass substrate, a light-transmissive indium tin oxide (ITO) substrate or the like may be used as the substrate 11 .
  • ITO indium tin oxide
  • a conductive material 13 is disposed on the PR layer 12 and the substrate 11 so as to form an electrode and so that a potential can be applied to a field emission material.
  • a metal capable of being used as an electrode in a semiconductor device is deposited on the PR layer 12 and the substrate 11 .
  • Any deposition method used in a general semiconductor manufacturing process may be used to deposit the conductive material 13 .
  • a vapor deposition method such as sputtering, ion beam deposition or evaporation, is used.
  • the conductive material 13 is deposited on the patterned PR layer 12 and the grooves 12 ′ so as to form a stepped surface.
  • the PR layer 12 and the contuctive material 13 are removed so that a conductive layer 14 remains on the substrate 11 .
  • a field emission material and metal nano powder are mixed at a desired ratio to form a mixture, and an exposed portion of the substrate 11 and the conductive layer 14 are coated with the mixture using spin coating or screen printing such that the mixture has a desired thickness.
  • a carbon-family material such as, carbon nanotubes
  • a necessary solvent is also mixed with the mixture. Consequently, a mixture layer 15 , composed of the field emission material and the metal nano powder, is formed on the exposed portion of the substrate 11 and the conductive layer 14 .
  • the metal nano power is used to increase an adhesion between the conductive layer 14 and the field emission material, so that a conductive fine powder is used as the metal nano powder.
  • metal nano powder having a size of a submicron to several microns (about 0.01 to 100 ⁇ m) is used, and may include several metal powders, such as Ag, Cu, Zn, Ni and the like, having low melting points.
  • the field emission material may be a carbon-family material, a metal, a semiconductor material, or the like.
  • the carbon-family material may be carbon nanotubes, a carbon horn, or the like.
  • the metal may be tungsten.
  • the semiconductor material may be Si. Palladium oxide (PLO) may also be used as the field emission material. Any material used as a general field emission material may be used as the field emission material according to an embodiment of the present invention.
  • the mixture layer 15 formed of the field emission material and the metal nano powder on the conductive layer 14 undergoes thermal treatment.
  • the solvent usually has a boiling point lower than a temperature for thermal treatment.
  • alcohol having a boiling point lower than the temperature for thermal treatment is preferably used as the solvent.
  • the thermal treatment is preferably performed at no more than 600° C., and a material having a boiling point lower than this temperature is preferably used as the solvent.
  • carbon nanotubes are used as the field emission material, most of the typically used solvents may be used as the solvent.
  • the metal and the field emission material excluding the solvent remain on the exposed portion of the substrate 11 and the conductive layer 14 .
  • the remaining metal adheres to the conductive layer 14 due to the thermal treatment, and the remaining field emission material sticks to the metal. Consequently, the remaining field emission material and the remaining metal form a mixture layer 15 ′.
  • the mixture layer 15 ′ formed on the substrate 11 and the conductive layer 14 undergoes surface processing.
  • the surface processing may be performed using a typically used method, and may use ultrasonic waves or an adhesive tape. Even when just an adhesive tape is used, the mixture layer 15 ′ formed on the conductive layer 14 has excellent adhesion to the conductive layer 14 .
  • the metal adheres to the conductive layer 14 due to the thermal treatment, and fixes the field emission material, which is mixed with the metal.
  • a plurality of protrusions 17 of the field emission material are formed on the mixture layer 15 ′ remaining after the thermal treatment. Consequently, the field emitter according to an embodiment of the present invention can be completely formed.
  • FIGS. 2A and 2B are pictures of a field emitter which is fabricated using carbon nanotubes as a field emission material in a method according to an embodiment of the present invention.
  • a conductive layer of a desired size is formed on a substrate 21 , and a mixture layer 22 composed of carbon nanotubes and metal nano powder is deposited on the conductive layer using spin coating or screen printing.
  • the substrate 21 is formed of ITO, and the metal nano powder is formed of Ag.
  • the conductive layer has a 2 ⁇ 2 cm size, and the mixture layer 22 is deposited on the conductive layer to have a 3 ⁇ 3 cm size.
  • FIG. 2B illustrates a specimen obtained by removing a solvent from a specimen of FIG. 2A using thermal treatment, and by performing surface processing on the specimen of FIG. 2A .
  • FIG. 2A when the mixture layer 22 formed on the substrate 21 undergoes surface processing, only a mixture layer 23 of 2 ⁇ 2 cm size adhering to an upper surface of the conductive layer remains on the substrate 21 . In other words, a portion of the mixture layer 22 excluding the mixture layer 23 of 2 ⁇ 2 cm size is removed by thermal treatment. This means that adhesion between the conductive layer and carbon nanotubes is significantly greater than adhesion between the substrate 21 and carbon nanotubes as described above.
  • FIGS. 3A and 3B are graphs showing measured electrical characteristics of a field emitter which uses carbon nanotubes as a field emission material, according to an embodiment of the present invention.
  • the field emitter according to an embodiment of the present invention when an identical potential is applied, the field emitter according to an embodiment of the present invention has greater field emission than conventional field emitters, namely, paste ( 1 ) and paste ( 2 ), that use carbon nanotubes as field emission materials.
  • paste ( 1 ) and paste ( 2 ) that use carbon nanotubes as field emission materials.
  • the field emitter according to the embodiment of the present invention emits a field of about 1200 ⁇ A/cm 2
  • the conventional field emitters emit a field of no more than 200 ⁇ A/cm 2 .
  • FIG. 3B is a graph showing field emission characteristics of field emitters versus a time during which the field emitters are used.
  • the size of a conventional field emitter continuously decreases according to the period of time during which the conventional field emitter is used.
  • the field emitter according to an embodiment of the present invention emits a small field that does not greatly vary according to the period of time during which the field emitter is used.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cold Cathode And The Manufacture (AREA)
US11/048,809 2004-02-05 2005-02-03 Method of manufacturing field emitter Expired - Fee Related US7507135B2 (en)

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Application Number Priority Date Filing Date Title
KR1020040007524A KR20050079339A (ko) 2004-02-05 2004-02-05 필드 에미터의 제조 방법
KR10-2004-0007524 2004-02-05

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JP (1) JP2005222952A (ko)
KR (1) KR20050079339A (ko)
CN (1) CN1652284A (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160225517A1 (en) * 2015-01-30 2016-08-04 Samsung Electro-Mechanics Co., Ltd. Electronic component, and method of manufacturing thereof

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US20080299298A1 (en) * 2005-12-06 2008-12-04 Electronics And Telecommunications Research Institute Methods of Manufacturing Carbon Nanotube (Cnt) Paste and Emitter with High Reliability
KR100911370B1 (ko) * 2005-12-06 2009-08-10 한국전자통신연구원 고 신뢰성 ｃｎｔ 페이스트의 제조 방법 및 ｃｎｔ 에미터제조 방법
CN101389411B (zh) * 2006-02-27 2010-12-01 东丽株式会社 组合物及使用该组合物的显示器部件的制备方法
CN101188179B (zh) * 2006-11-15 2010-05-26 清华大学 场发射电子源的制造方法
US11247504B2 (en) 2019-07-10 2022-02-15 Xerox Corporation Distributed parallel processing system for make-on-demand book manufacturing

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US20160225517A1 (en) * 2015-01-30 2016-08-04 Samsung Electro-Mechanics Co., Ltd. Electronic component, and method of manufacturing thereof
US11562851B2 (en) * 2015-01-30 2023-01-24 Samsung Electro-Mechanics Co., Ltd. Electronic component, and method of manufacturing thereof

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JP2005222952A (ja) 2005-08-18
US20050176336A1 (en) 2005-08-11
KR20050079339A (ko) 2005-08-10
CN1652284A (zh) 2005-08-10

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